Reaction of [RuNO(NO2)4OH]2– with Sulfamic Acid as a Pathway to Mixed Nitro Pyridine Ruthenium Nitrosyl Complexes. Issue 25 (9th August 2016)

• Record Type: Journal Article
• Authors: Kostin, Gennadiy A.; Mikhailov, Artem A.; Kuratieva, Nataliya V.; Tkachev, Sergey V.; Schaniel, Dominik; Woike, Theo
• Is Part Of: European journal of inorganic chemistry. Issue 25(2016)
• Page Start: 4045
• Page End: 4053
• Publication Date: 2016-08-09
• Subjects: Ruthenium -- N ligands -- Nitrogen oxides -- Isomerization; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201600477
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The transformations of [RuNO(NO2 )4 OH] 2– during sequential treatment with sulfamic acid and pyridine have been investigated by 15 N NMR spectroscopy. Depending on the initial molar ratio of Ru/NH2 SO3 H, the first stage of the reaction at room temperature in an aqueous solution proceeded with stoichiometric removal of one or two NO2 ligands and may be accompanied by ligand redistribution and partial isomerization NO2 /ONO. Further treatment with pyridine resulted in the replacement of labile ligands (H2 O, SO4 ) and the formation of mixed nitro pyridine complexes of ruthenium nitrosyl. Mixed nitrito‐ N ‐nitrito‐ O complexes PyH[RuNO(NO2 )2 (ONO)Py(OH)] and OC‐6‐34‐[RuNO(NO2 )(ONO)Py2 OH] as well as the dimeric ruthenium complex with µ‐bridging oxo groups NH4 [Ru(NO)Py3 (µ‐O)]2 (PF6 )3 were separated as solids and structurally characterized. The photochemical isomerization (445 nm, 9 K) of Ru–NO with the formation of metastable isonitrosyl complexes was found for all the prepared compounds; the population of the metastable state did not exceed 20 %. Abstract : The transformations of [RuNO(NO2 )4 OH] 2– during sequential treatment with sulfamic acid and pyridine have been investigated by 15 N NMR spectroscopy. The structures of the final mixed amine‐nitrito‐ N (nitrito‐ O ) complexes have been determined by X‐ray diffraction analysis.